Aqueous polyurethane dispersions

ABSTRACT

An aqueous polyurethane dispersion comprising at least one isocyanate terminated polyurethane prepolymer prepared by reacting in the presence of at least one pyrrolidone selected from the group consisting of N-n-butylpyrrolidone, N-isobutylpyrrolidone, N-sec-butylpyrrolidone and N-tert-butylpyrrolidone, a mixture (M) which comprises: at least one polyisocyanate compound (a), at least one polyol compound (b), having a molecular weight Mw of 200 to 8000 and a hydroxyl functionality of 1.5 to 6, and at least one water dispersible enhancing component having at least one hydrophilic group or potentially hydrophilic group in water.

FIELD OF INVENTION

The present invention relates to aqueous polyurethane dispersions usingat least a N—(C₄-alkyl)-pyrrolidone as a prepolymer diluent, adispersing agent and a coalescing agent wherein said aqueouspolyurethane dispersions are very useful for the manufacture of filmsand coatings. The invention further relates to said polyurethane-basedfilms and coatings and a process for the manufacturing thereof. Theinvention also relates to a process for the manufacturing of saidaqueous polyurethane dispersions.

BACKGROUND OF THE INVENTION

Aqueous polyurethane dispersions (PUDs) are well known and have mainlybeen developed due to the evolution of legislation towards reducing theVOC (volatile organic concentration) and the creation of environmentallyfriendly products. Water-based or waterborne PUDs have gained increasingimportance in a range of applications, due in large part to propertiessuch as adhesion to a range of substrates, resistance to chemicals,solvents and water, abrasion resistance and flexibility. Water-based PUDshow very good mechanical and chemical properties and match theregulatory restrictions for low volatile organic compound (VOC)containing raw paints.

Some efforts have also been directed to the development of substantiallysolvent-free aqueous polyurethane dispersions such as notably describedin U.S. Patent Application Publication No. 2011/0306724 A1. Saidsolvent-free aqueous polyurethane dispersions are characterized bysubstantially no emission of volatile organic materials.

Aqueous polyurethane dispersions (PUDs) are thus used in the productionof a variety of useful polyurethane products for example adhesives,sealants and coatings for various substrates including textile fabrics,plastic, wood, glass fibers, metals and the like. Chemical resistance,abrasion resistance, toughness, tensile strength, elasticity anddurability are among the many desirable properties of these coatings.Their main advantages are the versatility of polyurethane (PU) systemsand their effectiveness in producing ‘tailor-made’ coatings for a widerange of demanding applications. This results from the wide diversity ofraw-materials which can be combined in different ways during thesynthesis.

Several processes have been developed for the synthesis of PUD. All ofthese have a common first step, in which a medium molecular weightpolymer (i.e. prepolymer) is formed by the reaction of suitable diols orpolyols, in particular polyether, polyester or polycarbonate polyolswith a molar excess of diisocyanates or polyisocyanates. Said prepolymerneeds to be stabilized in order to allow its dispersion in water. Thereare two ways of stabilization, the first one consists of polymersstabilized by external emulsifiers, and the second one achievesstabilization by including hydrophilic centers in the polymer. Suchhydrophilic centers may be one of three types: non-ionic, cationic andanionic groups. These hydrophilic groups fulfil the function as internalemulsifiers and make it possible to produce stable water-basedemulsions. Thus, water-based PUDs are classified into anionic, cationicand nonionic systems.

U.S. Pat. No. 4,237,264 to Noll et al. and U.S. Pat. No. 4,238,378 toMarkusch et al. notably describe that for coating applications, thepolyurethane polymers can be stably dispersed in water by incorporatingsaid hydrophilic groups or potentially hydrophilic groups into theirbackbone.

The industrial production of PUDs is nowadays a well-establishedtechnology. There are two main synthetic routes to produce PUDs: theacetone process and the pre-polymer process.

Jansson R. C. described in TECHNICAL INFORMATION. LEAFLET NO 0127.January 2004. Pages 1 (11) to 11 (11)) that the pre-polymer mixingprocess is a versatile and straightforward process for the preparationsfor PUDs, thereby permitting a great variation in PU formulations. Thisbeing said, the selection and the relative amounts of the polyurethane(PU) constitutional components (i.e. isocyanate, polyol component, chainextenders, emulsifiers, in particular internal emulsifiers, organicsolvents, water, etc.), in the PUD formulation are thereby important forthe targeted coating properties. This is also described by Clausson A.et al. in Paint and Coatings Industry, January 2007, Vol. 23, Issue 1,page 30.

N-Methylpyrrolidone (NMP) has frequently been used as the organicsolvent in the preparation of PUDs. However, NMP is now known to causereproductive toxicity (it is considered as being reprotoxic) and isbeing labeled in the EU as “reprotoxic category 2” as from the 1st ofDecember 2010. Formulations containing >0.3% of NMP have to be labelledas such. Consequently, the use of the solvent is restricted toprofessional users. NMP has been placed on the REACH “Substance of VeryHigh Concern” (SVHC) list and is expected, sooner or later, to be placedunder authorization or restriction.

Despite the efforts that have been directed to the development ofsubstantially solvent-free aqueous polyurethane dispersions, asmentioned above, it remains an advantage to carry out the prepolymermixing process in the presence of organic solvents or non-reactivediluents with the first aim to control the viscosity of the prepolymer.It is known that said organic solvent remains as a co-solvent in thedispersion thereby affecting the final properties of the aqueouspolyurethane dispersions and articles, in particular coated articlesmade therefrom. Thus, the selection of the organic solvent is steered bythe targeted properties of the aqueous polyurethane dispersions andarticles made therefrom and by environmental legislation.

Therefore, there is still a need for environmentally friendly organicsolvents especially suitable for use in polyurethane (PU) systems havingan improved versatility, whereby said organic solvents can servemultiple purposes at the same time, in particular (1) acting as aprepolymer diluent in aqueous polyurethane dispersions (i.e. controllingthe viscosity of the prepolymer), (2) acting as a dispersing agent (i.e.providing an improved stability of the PUD) and (3) acting as acoalescing agent thereby aiding in the formation of smooth, uniformfilms and coatings. There is thus an ongoing need for improved aqueouspolyurethane dispersions comprising said organic solvents, present inminimal amounts which can provide products that are both chemically andcolloidally stable, containing minimal amounts of internal and/orexternal water dispersible entities, that do not emit VOC, particularlyPUDs having an improved ability to coalesce to films or coatings wherebysaid films and coatings obtained have improved mechanical properties, inparticular tensile strength and elongation, better tear resistance andimproved water resistance, and improved chemical resistance properties.

SUMMARY OF THE INVENTION

The inventors have now found surprisingly that it is possible to providean aqueous polyurethane dispersion fulfilling the above mentioned needs.

It is thus an object of the present invention to provide an aqueouspolyurethane dispersion comprising:

-   -   A. at least one isocyanate terminated polyurethane prepolymer        [prepolymer (P), herein after] prepared by reacting in the        presence of at least one pyrrolidone [(b-pyrrolidone, herein        after] selected from the group consisting of        N-n-butylpyrrolidone, N-isobutylpyrrolidone,        N-sec-butylpyrrolidone and N-tert-butylpyrrolidone, a        mixture (M) which comprises:        -   (a) at least one polyisocyanate compound (a),        -   (b) at least one polyol compound (b), having a molecular            weight M_(w) of 200 to 8000 and a hydroxyl functionality of            1.5 to 6,        -   (c) at least one water dispersible enhancing component            having at least one hydrophilic group or potentially            hydrophilic group [component (WD_(H)), herein after] and            comprising:            -   i. x mmol/kg of at least one water dispersible enhancing                compound having at least one anionic hydrophilic group                or potentially anionic hydrophilic group [compound                (WD_(HA)), herein after], and/or            -   ii. y mmol/kg of at least one water dispersible                enhancing compound having at least one non-ionic                hydrophilic group or potentially non-ionic hydrophilic                group [compound (WD_(HN)) herein after], and/or            -   iii. z mmol/kg of at least one water dispersible                enhancing compound having at least one cationic                hydrophilic group or potentially cationic hydrophilic                group [compound (WD_(HC)), herein after],            -   iv. w mmol/kg of at least one water dispersible                enhancing compound having at least one zwitterionic                hydrophilic group or potentially zwitterionic                hydrophilic group [compound (WD_(HZ)), herein after],            -   wherein

$\frac{{200x} + {70y} + {72z} + {75w}}{x + y + z + w} < {x + y + z + w} < \frac{{560x} + {248y} + {165z} + {300w}}{x + y + z + w}$

and at least one of x, y, z or w is different from 0 and all mmol/kg arebased on the weight of all the components initially present in themixture (M),

-   -   B. optionally, at least one isocyanate-reactive compound        [compound (I)] herein after], different from the polyol        compound (b) and different from the component (WD_(H)), having        reactive groups chosen among alcoholic hydroxyl groups or        primary or secondary amino groups; and    -   C. water.

It is a further object of the present invention to provide a method ofproducing said aqueous polyurethane dispersion.

It is also a further object of the present invention to provide films orcoatings obtained from said aqueous polyurethane dispersion.

It is also a further object of the present invention to provide a numberof uses of the b-pyrrolidone.

The aqueous polyurethane dispersion

Within the context of the present invention, the expression “at leastone pyrrolidone (b-pyrrolidone, herein after]” is intended to denote oneor more than one b-pyrrolidone.

As said, the prepolymer (P) in the aqueous polyurethane dispersion ofthe present invention is prepared by reacting a mixture (M) in thepresence of at least one b-pyrrolidone. Most preferred b-pyrrolidone isN-n-butylpyrrolidone.

The b-pyrrolidone of the present invention, as detailed above, is knownfor its use as a non-reprotoxic solvent as notably described in WO2013/107822, the whole content of which is herein incorporated byreference.

The inventors have now found that the b-pyrrolidone of the presentinvention, in particular N-n-butylpyrrolidone, brings the significantadvantage of a dramatically reduced toxicity of the aqueous polyurethanedispersion according to the invention, and thus also of the derivedpolyurethane films or coatings.

WO 2005/090430 A1 and DE 10 2007 028890 A1 describe the use ofN-(cyclo)-alkylpyrrolidones with (cyclo)alkyl radicals having 2 to 6 Catoms, in particular N-ethylpyrrolidone (NEP), as solvents in processesfor preparing polyurethane dispersions. However, according to Annex VIof CLP [i.e. the Regulation on classification, labelling and packagingof substances and mixtures. This Regulation aligns previous EUlegislation on classification, labelling and packaging of chemicals tothe GHS (Globally Harmonised System of Classification and Labelling ofChemicals)], NEP is also classified as reprotoxic.

WO 2005/090430 A1 and DE 10 2007 028890 A1 state that the use ofN-(cyclo)-alkylpyrrolidones with (cyclo)alkyl radicals having 2 to 6 Catoms, in particular N-ethylpyrrolidone (NEP), has a beneficial effecton the properties of the resultant polyurethane dispersion. However,these documents do not disclose any experimental results demonstratingthat the alleged beneficial effect was actually obtained. On thecontrary, NEP for example does not allow the formation of a truenon-ionic polyurethane dispersion system but forms instead a coagulatedgel, as illustrated in the exemplified section below. Further, WO2005/090430 A1 and DE 10 2007 028890 A1 remain completely silent aboutthe multipurpose functions of N-(cyclo)alkylpyrrolidones with(cyclo)alkyl radicals having 2 to 6 C atoms, being a diluent, adispersing agent and a coalescing agent for PU systems.

The inventors have now surprisingly found that the specific selection ofthe b-pyrrolidone, as detailed above, brings the advantage that saidb-pyrrolidone may serve multiple functions and provides at the same time(1) an improved viscosity control in the prepolymer (P), as detailedabove (2) an improved dispersion ability of the aqueous polyurethanedispersion and (3) an improved ability of the aqueous polyurethanedispersion to coalesce to a film or a coating.

In a preferred embodiment of the present invention, the weight percentof the b-pyrrolidone, as detailed above, relative to the total weight ofall the components initially present in the mixture (M) and theb-pyrrolidone is generally less than 50 wt. %, preferably less than 40wt. %, more preferably less than 30 wt. %, even more preferably lessthan 25 wt. %.

It is further understood that the weight percent of the b-pyrrolidone,relative to the total weight of all the components initially present inthe mixture (M) and the b-pyrrolidone is generally greater than 1 wt. %,preferably greater than 4 wt. %, more preferably greater than 6 wt. %,even more preferably greater than 8 wt. %.

Good results were obtained when the weight percent of the b-pyrrolidone,relative to the total weight of all the components initially present inthe mixture (M) and the b-pyrrolidone is between 8 wt. %-25 wt. %.

The b-pyrrolidone, as detailed above, is generally mixed into themixture (M) of the present invention and is carried through to the waterphase as part of the aqueous polyurethane dispersion.

Advantageously, the weight percent of the b-pyrrolidone, relative to thetotal weight of the aqueous polyurethane dispersion is less than 20 wt.%, preferably less than 12 wt. %, more preferably less than 8 wt. %.

Thus, the inventors have surprisingly found that the b-pyrrolidone ofthe present invention can be used as a good diluent to render theviscosity of mixture (M), as detailed above, low enough to achieveexcellent processing properties in the manufacturing of the prepolymer(P) while improving at the same time the toxicological properties of theprepolymer (P) and the final aqueous polyurethane dispersion.

According to certain embodiments of the present invention, theprepolymer (P) is prepared by reacting the mixture (M), as detailedabove, in the sole presence of the b-pyrrolidone as organic solvent.This being said, the mixture (M) is thus substantially free of anyadditional organic solvent.

For the purpose of the present invention, the term “additional solvent”is understood to denote any solvent different from the b-pyrrolidone anddifferent from the ingredients of the mixture (M).

For the purpose of the present invention, the expression “substantiallyfree of any additional organic solvent” means that the additionalorganic solvent content, relative to the total weight of all thecomponents initially present in the mixture (M), is less than 0.01 wt.%, in particular less than 0.005 wt. %, specifically less than 0.001 wt.%, more specifically less than 0.0005 wt. %, even more specifically lessthan 0.0001 wt. %.

According to other embodiments of the present invention, the theb-pyrrolidone is used together with an additional solvent in themanufacturing of the prepolymer (P) wherein said additional solvent ispresent in an amount of at most 20% by weight, preferably of at most 15%by weight and more preferably of at most 10% by weight, relative to thetotal weight of the b-pyrrolidone.

Non-limiting examples of suitable additional solvents may include, butare not limited to, acetone, methyl ethyl ketone, propylene glycol,ethylene glycol monobutyl ether, diethylene glycol monobutyl ether,propylene glycol butyl ether, dipropylene glycol butyl ether,dipropylene glycol methyl ether, propylene glycol methyl ether andpropylene glycol methyl ether actetate.

As said, the mixture (M) of the present invention comprises at least onepolyisocyanate compound (a).

Within the context of the present invention the expression “at least onepolyisocyanate compound (a)” is intended to denote one or more than onepolyisocyanate compound (a).

For the purpose of the present invention, the expression “polyisocyanatecompound (a)” refers to any polyisocyanate commonly used in themanufacturing of aqueous polyurethane dispersions.

Said polyisocyanate compound (a) may include notably aliphatic,cycloaliphatic, araliphatic and aromatic diisocyanates andpolyisocyanates. Cycloaliphatic diisocyanates are in particularpreferred.

Non-limiting examples of suitable aliphatic diisocyanates may include,but not limited to, tetramethylene diisocyanate, hexamethylenediisocyanate (1,6-diisocyanatohexane); octamethylene diisocyanate;decamethylene diisocyanate; dodecamethylene diisocyanate;tetradecamethylene diisocyanate; trimethylhexane diisocyanate;tetramethylhexane diisocyanate and mixtures thereof.

Preferred aliphatic diisocyanates include trimethylhexane diisocyanateand hexamethylene diisocyanate.

Non-limiting examples of suitable cycloaliphatic diisocyanates mayinclude, but not limited to, isophorone diisocyanate (IPDI);4,4′-methylenebis(cyclohexyl isocyanate) (H12MDI); 1,4-, 1,3- or1,2-diisocyanatocyclohexane; 2,2-bis(4-isocyanatocyclohexyl)propane;1,3-bis(isocyanatomethyl)cyclohexane;2,4-diisocyanato-1-methylcyclohexane;2,6-diisocyanato-1-methylcyclohexane and mixtures thereof.

Preferred cycloaliphatic diisocyanates include isophorone diisocyanate(IPDI); 4,4′-methylenebis(cyclohexyl isocyanate) (H12MDI); IPDI andH12MDI are particularly preferred.

Non-limiting examples of suitable araliphatic diisocyanates may include,but not limited to, m-tetramethyl xylylene diisocyanate (m-TMXDI);p-tetramethyl xylylene diisocyanate; and mixtures thereof.

A preferred araliphatic diisocyanate is notably m-tetramethyl xylylenediisocyanate (m-TMXDI).

Non-limiting examples of suitable aromatic diisocyanates may include,but not limited to, 2,4- and 2,6-tolylene diisocyanate and the isomermixtures thereof; m- or p-xylylene diisocyanate;2,4′-diisocyanatodiphenylmethane and 4,4′-diisocyanatodiphenylmethane(MDI, 4,4′-methylene diphenyl diisocyanate) and the isomer mixturesthereof; 1,3- and 1,4-phenylene diisocyanate; 1,5-naphthylenediisocyanate; diphenylene 4,4′-diisocyanate; 1,4-diisocyanatobenzene;diphenyl ether 4,4′-diisocyanate;4,4′-diisocyanato-3,3′-dimethylbiphenyl, 3-methyldiphenylmethane4,4′-diisocyanate and mixtures thereof.

Preferred aromatic diisocyanates include 2,4- and 2,6-tolylenediisocyanate and 2,4′-diisocyanatodiphenylmethane and4,4′-diisocyanatodiphenylmethane (MDI, 4,4′-methylene diphenyldiisocyanate)

Non-limiting examples of suitable polyisocyanates may include, but notlimited to, polyphenyl polymethylene polyisocyanates (PMDI, polymericMDI) and polyether modified PMDI; mixtures of PMDI and toluenediisocyanates; modified multifunctional isocyanates, such as notablypolyisocyanates containing esters, ureas, biurets, allophanates,carbodiimides and/or uretonimines.

As said, the mixture (M) of the present invention comprises at least onepolyol compound (b) having a molecular weight M_(w) of 200 to 8000 g/moland a hydroxyl functionality of 1.5 to 6.

Within the context of the present invention the expression “at least onepolyol compound (b) having a molecular weight M_(w) of 200 to 8000 g/moland a hydroxyl functionality of 1.5 to 6” is intended to denote one ormore than one polyol compound (b) having a molecular weight M_(w) of 200to 8000 g/mol and a hydroxyl functionality of 1.5 to 6.

The polyol compound (b) has preferably a molecular weight M_(w) of 400to 6000 g/mol, more preferably 400 to 4000 g/mol and even morepreferably 400 to 3500 g/mol.

The polyol compound (b) has preferably a hydroxyl functionality of 1.5to 3.5 and more preferably a hydroxyl functionality of 1.9 to 2.1.

Non-limiting examples of the polyol compound (b) that can suitably beused for the preparation of the prepolymer (P) of the present inventionmay include for example conventional polyester polyols, polyacrylatepolyols, polyurethane polyols, polycaprolactone polyols, polycarbonatepolyols, polyether polyols, polyester polyacrylate polyols andpolyurethane polyacrylate polyols, polyurethane polyester polyols,polyurethane polyether polyols, polyurethane polycarbonate polyols,polyester polycarbonate polyols, and mixture thereof.

Among polyether polyols mention may be made of the polyaddition productsof styrene oxide, ethylene oxide, propylene oxide, tetrahydrofuran,butylene oxide, epichlorohydrin, and the co-addition and graft productsthereof, as well as the polyether polyols obtained by condensation ofpolyhydric alcohols or mixtures thereof and by alkoxylation ofpolyhydric alcohols, amines and amino alcohols.

Polyether polyols based on propylene oxide and optionally ethylene oxidewith a molecular weight between 200 and 6000, an average hydroxylfunctionally between 1.5 and 3.5 preferably between 1.9 and 2.1 and anoxypropylene content between 10 and 100% more preferably between 75 and100% are examples of suitable polyol compounds (b). The production ofthese polyols and the way to control their average equivalent weightsand functionalities is well known in the art.

Among polyester polyols mention may be made of polycondensates ofpolyhydric alcohols and polycarboxylic acids, also including the naturaloil based polyester polyols such as notably castor oil. Instead of thefree polycarboxylic acids it is also possible to use the correspondingpolycarboxylic anhydrides or corresponding polycarboxylic esters oflower alcohols, or mixtures thereof, to prepare the polyester polyols.The polycarboxylic acids can be aliphatic, cycloaliphatic, araliphatic,aromatic or heterocyclic and can be optionally substituted, by halogenatoms, for example, and/or unsaturated. Examples are suberic, azelaic,phthalic, and isophthalic acid, phthalic, tetrahydrophthalic,hexahydrophthalic, tetrachlorophthalic, endomethylenetetrahydrophthalic,glutaric and maleic anhydride, maleic acid, fumaric acid, dimeric fattyacids and fatty acids. Preference is given to dicarboxylic acids of thegeneral formula HOOC—(CH₂)_(y)—COOH, where y is a number from 1 to 20,preferably an even number from 2 to 20, examples being succinic, adipic,sebacic and dodecane-dicarboxylic acids.

Examples of suitable polyhydric alcohols are ethylene glycol,bis(hydroxymethyl)cyclohexanes, 1,2-propanediol, 1,3-propanediol,1,3-butanediol, 1,4-butenediol, 1,4-butynediol, 1,5-pentanediol,neopentyl glycol, 2-methyl-1,3-propanediol and also diethylene glycol,triethylene glycol, tetraethylene glycol, polyethylene glycol,dipropylene glycol, polypropylene glycol, dibutylene glycol andpolybutylene glycols. Preference is given to alcohols of the generalformula HO—(CH₂)_(x)—OH, where x is a number from 1 to 20, preferably aneven number from 2 to 20. Examples of such alcohols are ethylene glycol,1,4-butanediol, 1,6-hexanediol, 1,8-octanediol and 1,12-dodecanediol.

The commercially available Piothane® polyester polyols from PioneerResins are typical examples of polyester polyols suitable for theinvention.

Among polycarbonate polyols mention may be made of reaction products ofcarbonic acid derivatives, for example diphenyl carbonate, dimethylcarbonate or phosgene, with diols. Examples of such diols are ethyleneglycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butane diol,1,6-hexanediol, 1,8-octanediol, neopentyl glycol,1,4-bis(hydroxymethyl)cyclohexane, 2-methyl-1,3-propanediol,2,2,4-trimethylpentanediol, 1,3-dipropylene glycol, polypropyleneglycols, dibutylene glycol, polybutylene glycols, bisphenol A,tetrabromobisphenol A but also lactone-modified diols such as notablyε-caprolactone.

Mention may also be made of reaction products of caprolactone copolymerswith polylactide, polyether, polyester, hydrophilic glycol andpolycarbonate.

The commercially available Capa™ Polyols from Perstorp are typicalexamples of polycaprolactone polyols and polycaprolactone polycarbonatecopolymer diols suitable for the invention. In particular, thecommercially available CAPA™7203 polycaprolactone/polycarbonatecopolymer ester is a suitable polyester polyol.

The inventors have found that the use of the b-pyrrolidone, inparticular N-n-butylpyrrolidone, which also acts as a good dispersingagent, enables significant reduction of the content of water dispersibleentities (i.e. component c) in mixture (M)) in the preparation of theprepolymer (P) of the present invention.

This being said, due to the presence of the b-pyrrolidone in the mixture(M) for the preparation of the prepolymer (P) comprised in the aqueouspolyurethane dispersion of the present invention, the at least one waterdispersible enhancing component having at least one hydrophilic group orpotentially hydrophilic group [component (WD_(H)), herein after] iscomprising:

-   -   i. x mmol/kg of at least one water dispersible enhancing        compound having at least one anionic hydrophilic group or        potentially anionic hydrophilic group [compound (WD_(HA)),        herein after], and/or    -   ii. y mmol/kg of at least one water dispersible enhancing        compound having at least one non-ionic hydrophilic group or        potentially non-ionic hydrophilic group [compound (WD_(HN))        herein after], and/or    -   iii. z mmol/kg of at least one water dispersible enhancing        compound having at least one cationic hydrophilic group or        potentially cationic hydrophilic group [compound (WD_(HC)),        herein after],    -   iv. w mmol/kg of at least one water dispersible enhancing        compound having at least one zwitterionic hydrophilic group or        potentially zwitterionic hydrophilic group [compound (WD_(HZ)),        herein after],    -   wherein

$\frac{{200x} + {70y} + {72z} + {75w}}{x + y + z + w} < {x + y + z + w} < \frac{{560x} + {248y} + {165z} + {300w}}{x + y + z + w}$

preferably

$\frac{{240x} + {90y} + {85z} + {110w}}{x + y + z + w} < {x + y + z + w} < \frac{{400x} + {200y} + {150z} + {250w}}{x + y + z + w}$

-   -   and at least one of x, y, z or w is different from 0 and all        mmol/kg are based on the weight of all the components initially        present in the mixture (M).

Within the context of the present invention the expression “at least onewater dispersible enhancing component having at least one hydrophilicgroup or potentially hydrophilic group [component (WD_(H)), hereinafter]” is intended to denote one or more than one component (WD_(H)).It is understood that the same applies for the expressions “compound(WD_(HA))”, “compound (WD_(HN))”, “compound (WD_(HC))” and compound(WD_(HZ)).

It is also further understood that for the purposes of the presentinvention a potentially hydrophilic group refers to a group which can beconverted into a hydrophilic group. In particular, the potentiallyanionic and cationic hydrophilic groups are groups that can, if desired,be converted to anionic and cationic hydrophilic groups, respectively,upon neutralizing with a neutralizing agent, as will be discussed indetail below.

The hydrophilic groups or the potentially hydrophilic groups of thecomponent (WD_(H)) react with the polyisocyanate compound (a) much moreslowly than do the functional groups (FG groups) of the component(WD_(H)) that are used to build up the polymer backbone chain of theprepolymer (P).

Suitable compounds (WD_(HA)) may be selected from compounds having thegeneral formula (HA):

FG-R¹-AG  formula (HA)

wherein FG is at least one functional group, wherein said functionalgroup is preferably selected from the group consisting of —OH, —SH, —NH₂or —NHR², wherein R² is an alkyl or aryl group, preferably R² isselected from the group consisting of methyl, ethyl, isopropyl,n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopentyl orcyclohexyl, R¹ is an aliphatic, cycloaliphatic or aromatic radicalcontaining 1 to 20 carbon atoms, and AG is at least one anionic orpotential anionic group wherein said anionic or potential anionic groupis selected from the group consisting of —COOY, —SO₃Y and —PO(OY)₂wherein each of Y, equal to or different from each other, is selectedfrom the group consisting of hydrogen, ammonium salt, alkali metal,alkaline earth metal.

Typical compounds (WD_(HA)) having the general formula (HA), as definedabove, notably include mercaptoacetic acid, mercaptopropionic acid,thiolactic acid, mercaptosuccinic acid, glycine, iminodiacetic acid,sarcosine, alanine, β-alanine, leucine, isoleucine, aminobutyric acid,hydroxyacetic acid, hydroxypivalic acid, lactic acid, hydroxysuccinicacid, hydroxydecanoic acid, dimethylolpropionic acid, hydroxydodecanoicacid, dimethylolbutyric acid, 12-hydroxystearic acid,ethylenediaminetriacetic acid, hydroxyhexadecanoic acid,aminonaphthalenecarboxylic acid, hydroxyethanesulfonic acid, taurine,mercaptopropanesulfonic acid, hydroxypropanesulfonic acid,mercaptoethanesulfonic acid, aminomethanesulfonic acid,aminopropanesulfonic acid and also the alkali metal, alkaline earthmetal or ammonium salts thereof.

Preferred compounds (WD_(HA)) are selected from those having theformulae (HA-1) to (HA-6):

HO—R³—CR⁴(COOY)—R⁵—OH  (HA-1)

HO—R³—CR⁴(—SO₃Y)—R⁵—OH  (HA-2)

HO—R³—CR⁴(—PO(OY)₂)—R⁵—OH  (HA-3)

H₂N—R³—CR⁴(—COOY)—R⁵—NH₂  (HA-4)

H₂N—R³—CR⁴(—SO₃Y)—R⁵—NH₂  (HA-5)

H₂N—R³—CR⁴(—PO(OY)₂)—R⁵—NH₂  (HA-6)

wherein each of R³ and R⁵, equal to or different from each other, is aC₁- to C₄-alkanediyl unit, each of R⁴, equal to or different from eachother, is a C₁- to C₄-alkyl unit and Y has the same meaning as definedabove.

More preferred compounds (WD_(HA)) are those having the formulae (HA-1),as specified above, wherein Y is an hydrogen.

Even more preferred compounds (WD_(HA)) are dimethylolbutyric acid(DMBA) and dimethylolpropionic acid (DMPA).

Most preferred compound (WD_(HA)) is dimethylolpropionic acid (DMPA).

Suitable compounds (WD_(HN)) may be selected from compounds having thegeneral formula (HN):

FG-R¹—Z—X—R′  formula (HN)

wherein FG is at least one functional group, wherein said functionalgroup is preferably selected from the group consisting of —OH, —SH, —NH₂or —NHR², wherein R² is an alkyl or aryl group, preferably R² isselected from the group consisting of methyl, ethyl, isopropyl,n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopentyl orcyclohexyl, R¹ is an aliphatic, cycloaliphatic or aromatic radicalcontaining 1 to 20 carbon atoms, X is a polyalkylene oxide chain having5 to 100, preferably 10 to 80 repeating alkylene oxide units, which maybe composed to an extent of at least 40%, preferably at least 65%, ofrepeating ethylene oxide units and which in addition to said repeatingethylene oxide units may be composed of propylene oxide, butylene oxideor styrene oxide units, Z is oxygen or —NR⁶—, wherein R⁶ is H, an alkylor aryl group, preferably R⁶ is selected from the group consisting ofmethyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl,tert-butyl, cyclopentyl or cyclohexyl and R′ is a monovalent hydrocarbonradical having 1 to 12 carbon atoms, preferably an unsubstituted alkylradical having 1 to 4 carbon atoms.

Typical compounds (WD_(HN)) having the general formula (HN), as definedabove, are notably described in U.S. Pat. No. 3,905,929 and U.S. Pat.No. 3,920,598, the entire content of which are herein incorporated byreference.

Preferred compounds (WD_(HN)) are having the general formula (HN-1), asdefined below,

(HO)₂—R⁷—O—X—R′  formula (HN-1)

wherein R⁷ is trivalent hydrocarbon radical having 3 to 12 carbon atoms,X and R′ have the same meaning as defined above.

Even more preferred compounds (WD_(HN)) are having the general formula(HN-1′):

wherein n is an integer of 10 to 25, preferably n is an integer of 16 to22.

Suitable compounds (WD_(HC)) may be selected from compounds having atleast one tertiary amino group or at least one quaternary amino group.

Non-limiting examples of suitable compounds (WD_(HC)) may include, butare not limited to, tris(hydroxyalkyl)amines,N,N′-bis(hydroxyalkyl)alkylamines, N-hydroxyalkyl-dialkylamines,tris(aminoalkyl)amines, N,N′-bis(aminoalkyl)alkylamines andN-aminoalkyl-dialkylamines, wherein each of said alkyl radical ordivalent alkyl radical, equal to or different from each other, isconsisting of 2 to 6 carbons. Polyethers containing tertiary nitrogenatoms and preferably two terminal hydroxyl groups, such as areobtainable in conventional manner by, for example, alkoxylating amineshaving two hydrogen atoms attached to amine nitrogen, examples beingmethylamine, aniline and N,N′-dimethylhydrazine may also suitably beused as compounds (WD_(HC)). Said polyethers generally have a molarweight of between 500 and 6000 g/mol.

For the purpose of the present invention, the term “water dispersibleenhancing compound having at least one zwitterionic hydrophilic group”refers to compounds having both at least one anionic and at least onecationic group within the same molecule. It is known that this occurs ata certain pH range, for example between 3 and 10.

It is also further understood that for the purposes of the presentinvention a potentially zwitterionic hydrophilic group refers to a groupwhich can be converted into a zwitterionic hydrophilic group bysubjecting the potentially zwitterionic hydrophilic group to theappropriate pH range.

Suitable compounds (WD_(HZ)) may be selected from compounds having bothi) a cationic group selected from the group consisting of a quaternaryammonium, a phosphonium, a sulfonium and ii) an anionic group selectedfrom a carboxylate, a sulfonate, a sulfate, a phosphate, and an oxide.

In particular, compounds (WD_(HZ)) may be selected among betains,preferably carboxy-betaines, sulfo-betaines, phospho-betaines andthetins.

Carboxy-betaines, sulfo-betaines, phospho-betaines are notably describedin U.S. Patent application 2014/0248232 the whole content is hereinincorporated by reference.

For the purpose of the present invention, betaines refers to zwitterionshaving a positively charged nitrogen atom, and thetins refers tozwitterions having a positively charged sulfur atom.

β-alanine betaine, N-butyldiethanolamine betaine are typical examples ofcarboxy-betaines.

N-butyldiethanolamine sulfopropyl betaine is a typical example of asulfo-betaine.

Non-limiting examples of suitable thetins are notably described in U.S.Pat. No. 3,573,049 the whole content is herein incorporated byreference.

According to certain preferred embodiments of the present invention, thecomponent (WD_(H)) present in the mixture (M) comprises, consistsessentially of:

i. x mmol/kg of the compound (WD_(HA)), and/or

ii. y mmol/kg of the compound (WD_(HN))

wherein

$\frac{{200x} + {70y}}{x + y} < {x + y} < \frac{{560x} + {248y}}{x + y}$

preferably,

$\frac{{240x} + {90y}}{x + y} < {x + y} < \frac{{400x} + {200y}}{x + y}$

and more preferably,

$\frac{{240x} + {90y}}{x + y} < {x + y} < \frac{{350x} + {150y}}{x + y}$

and at least one of x or y is different from 0 and all mmol/kg are basedon the weight of all the components initially present in the mixture(M).

For the purpose of the present invention, the expression “consistsessentially of” is intended to denote that any additional compounddifferent from the compound (WD_(HA)), as detailed above, and thecompound (WD_(HN)), as detailed above, is present in an amount of atmost 1% by weight, based on the total weight of the component (WD_(H)).

According to one particular embodiment of the present invention, thecomponent (WD_(H)) present in the mixture (M) comprises, preferablyconsists of, compound (WD_(HA)), as detailed above, and is present in amolar amount, based on the weight of all the components initiallypresent in the mixture (M), of 200 to 560 mmol/kg, preferably 240 to 400mmol/kg, more preferably 240 to 350 mmol/kg.

According to another particular embodiment of the present invention, thecomponent (WD_(H)) present in the mixture (M) comprises, preferablyconsists of, compound (WD_(HN)), as detailed above, and is present in amolar amount, based on the weight of all the components initiallypresent in the mixture (M), of 70 to 248 mmol/kg, preferably 90 to 200mmol/kg, and more preferably 90 to 150 mmol/kg.

According to another particular embodiment of the present invention, thecomponent (WD_(H)) present in the mixture (M) comprises, preferablyconsists of, compound (WD_(HC)), as detailed above, and is present in amolar amount, based on the weight of all the components initiallypresent in the mixture (M), of 72 to 165 mmol/kg, preferably 85 to 150mmol/kg, and more preferably 95 to 150 mmol/kg.

According to another particular embodiment of the present invention, thecomponent (WD_(H)) present in the mixture (M) comprises, preferablyconsists of, compound (WD_(HZ)), as detailed above, and is present in amolar amount, based on the weight of all the components initiallypresent in the mixture (M), of 75 to 300 mmol/kg, preferably 110 to 250mmol/kg, and more preferably 110 to 150 mmol/kg.

As mentioned above, the anionic and cationic hydrophilic groups can beformed by neutralizing the corresponding potential anionic and cationichydrophilic groups with at least one neutralizing agent.

Within the context of this invention, the term “neutralizing agents” isintended to denote all types of agents which are useful for convertingsaid potential anionic and cationic hydrophilic groups to thecorresponding anionic and cationic hydrophilic groups.

Non-limiting examples of neutralizing agents suitable for converting thepotential anionic hydrophilic group into the corresponding anionichydrophilic group, in particular neutralizing acid groups such ascarboxylic acid and sulfonic acid groups, include inorganic alkalimetals bases such as potassium hydroxide, sodium hydroxide, and lithiumhydroxide; ammonia, primary amines, secondary amines, or tertiaryamines. Tertiary amines are especially preferred.

Suitable neutralizing agents having basic tertiary amino groups arenotably described in patent application US 2011/0306724 A1, the wholecontent is herein incorporated by reference.

Among tertiary amines suitable to use as neutralizing agents mention canbe made of triethylamine, trimethylamine, triisopropylamine,tributylamine, N,N-dimethyl-cyclohexylamine, N,N-dimethyl-ethanolamine,N,N-diethyl-ethanolamine, triethanolamine, N-methyl-diethanolamine,dimethylaminopropanol, and 2-(methoxyethyl)dimethylamine. Triethylamineand N,N-dimethyl-ethanolamine are in particular preferred.

Non-limiting examples of neutralizing agents suitable for converting thepotential cationic hydrophilic group into the corresponding cationichydrophilic group, in particular neutralizing the tertiary amino group,include inorganic acids such as notably phosphoric acid, sulfuric acid,hydrohalic acids (e.g. hydrochloric acid) or nitric acid; organic acids,such as notably formic acid, acetic acid or lactic acid, or by reactionwith appropriate quaternizing agents such as notably C₁ to C₆ alkylhalides into the ammonium salts.

Said neutralization or quaternization may be conducted before, during orafter the preparation of the prepolymer (P), as detailed above. Whenadded after the preparation of the prepolymer (P), the neutralizingagent may be added directly after the formation of the prepolymer (P)but prior to dispersing said prepolymer (P) in water or after dispersingsaid prepolymer (P) in water, thus during the production of polyurethanedispersion.

Conducting the neutralization step after the formation of the prepolymer(P), but prior to dispersing said prepolymer (P) in water advantageouslyprovide a better dispersiblity of the prepolymer (P) in water comparedto adding the neutralizing agent to the water in the dispersing step.

The stoichiometry of the mixture (M) of the present invention is suchthat the polyisocyanate compound (a) is present in excess.

According to a preferred embodiment of the present invention, the molaramount of the polyisocyanate compound (a) is chosen such that the molaramount of the isocyanate groups (NCO groups) of the polyisocyanatecompound (a) relative to the molar amount of the isocyanate reactivegroups of all the compounds initially present in the mixture (M) is from1.05 to 3, preferably from 1.3 to 2.5, more preferably from 1.5 to 2.0.

It is further understood that the isocyanate reactive groups include thefunctional groups (FG) of the component (WD_(H)), as mentioned above,being different from the hydrophilic groups or the potentiallyhydrophilic groups of the component (WD_(H)), which are able to reactwith the isocyanate groups of the polyisocyanate compound (a).

In an advantageous embodiment of the present invention, the prepolymer(P) prepared by reacting the mixture (M) in the presence of theb-pyrrolidone, comprises unreacted NCO groups in an amount of at most15% by weight (% wt.), preferably at most 10% wt., more preferably atmost 8% wt., relative to total weight of the prepolymer (P).

As said, the aqueous polyurethane dispersion of the present inventionmay optionally further comprise at least one isocyanate-reactivecompound [compound (I)] herein after], different from the polyolcompound (b) and different from the component (WD_(H)), having reactivegroups chosen among alcoholic hydroxyl groups or primary or secondaryamino groups.

When present, compound (I) may be added before, during (e.g. as acompound of mixture (M)) or after the preparation of the prepolymer (P)of the present invention.

In one embodiment of the present invention, the compound (I) isimmediately added after the preparation of the prepolymer (P) therebyforming a polyurethane polymer [polymer (PU), herein after] wherein saidpolymer (PU) is dispersed in water.

In a preferred embodiment of the present invention, the compound (I) isadded after dispersing the prepolymer (P), as mentioned above, in water.Thus, the compound (I) is added during the production of the aqueouspolyurethane dispersion.

Within the context of the present invention the mention “at least oneisocyanate-reactive compound [compound (I)] herein after]” is intendedto denote one or more than one component (I).

Said compound (I) can be used for crosslinking or chain extension of theprepolymer (P), as detailed above.

Any chain extender and/or crosslinking agent, different from the polyolcompound (b) and the component (WD_(H)), known to the skilled person inthe art for the manufacturing of polyurethanes can be used in thisinvention.

According to an advantageous embodiment of the present invention, theaqueous polyurethane dispersion comprises the compound (I) in a molaramount of at most 10%, preferably at most 8%, more preferably of at most5%, relative to the total molar amount of the polyol compound (b) andthe component (WD_(H)).

According to a preferred embodiment of the present invention, theaqueous polyurethane dispersion comprises the compound (I), when addedafter the preparation of the prepolymer (P), in a molar amount which ischosen as such that the molar amount of the isocyanate reactive groupsin the compound (I) relative to the molar amount of the unreacted NCOgroups in the prepolymer (P) is from 3:1 to 1:3, preferably 2:1 to 1:2,more preferably 1.5:1 to 1:1.5.

In general, compound (I) is selected from the group consisting of diolshaving a molecular weight M_(w) of 60 to 200 g/mol, polyfunctionalalcohols, amines having at least 2 primary and/or secondary aminogroups, mono-alcohols having at least 1 primary and/or secondary aminogroups.

Among diols having a molecular weight M_(w) of 60 to 200 g/mol mentioncan notably be made of 1,4-butanediol, 1,3-butanediol, hexanediol,methyl propanediol, butylethyl propane diol, hydroquinonebis(2-hydroxyethyl)ether, 2,2′-(phenylimino)diethanol, anddiethanol-para-toluidinepentaerythritol.

Among polyfunctional alcohols mention can notably be made oftrimethylolbutane, trimethylolpropane, trimethylolethane, ethyleneglycol, diethylene glycol, propylene glycol, glycerol, sugar alcohols,such as sorbitol, mannitol, diglycerol, threitol, erythritol, adonitol(ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), maltitolor isomalt.

Among amines having at least 2 primary and/or secondary amino groupsmention can notably be made of diamines such as ethylenediamines,propylenediamines, butylenediamines, diaminohexanes, piperazine,2,5-dimethylpiperazine, hydrazine, hydrazine hydrate,amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine,IPDA), 4,4′-diaminodicyclohexylmethane, aminoethylethanolamine,1,4-diamino-cyclohexane; triamines such as diethylenetriamine or1,8-diamino-4-aminomethyloctane; higher amines such astriethylenetetramine, tetraethylenepentamine; polymeric amines such aspolyethylenamines. Diamines, in particular ethylenediamine, hydrazine orhydrazine hydrate (i.e. 64% hydrazine concentration in water) andtriamines, in particular diethylenetriamine, and mixture thereof areespecially preferred.

In general, amines having at least 2 primary and/or secondary aminogroups react more quickly with isocyanates than do alcohols or water.Therefore, the prepolymer (P) is advantageously first dispersed in waterand then subjected to chain extension or crosslinking by adding saidamines. Said amines are advantageously mixed with water.

Among mono-alcohols having at least 1 primary and/or secondary aminogroups mention may be made of mono-ethanolamine and amino methylpropanol.

According to certain embodiments of the present invention, the aqueouspolyurethane dispersion can further comprise at least one isocyanatemonofunctional reactive compound.

Non-limiting examples of suitable isocyanate monofunctional reactivecompound may include methanol, ethanol, isopropanol, n-propanol,n-butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycolmonomethyl ether, ethylene glycol monoethyl ether, 1,3-propanediolmonomethyl ether, n-hexanol, n-heptanol, n-octanol, n-decanol,n-dodecanol (lauryl alcohol) and 2-ethylhexanol.

When present, the isocyanate monofunctional reactive compound may beadded before, during or after the preparation of the prepolymer (P), asdetailed above. When added after the preparation of the prepolymer (P),the isocyanate monofunctional reactive compound may be added directlyafter the formation of the prepolymer (P) but prior to dispersing saidprepolymer (P) in water or after dispersing said prepolymer (P) inwater, thus during the production of the aqueous polyurethanedispersion.

When present, the isocyanate monofunctional reactive compound is presentin a molar amount of at most 1%, preferably at most 0.5%, morepreferably of at most 0.02%, relative to the molar amount of theisocyanate groups (NCO groups) of the polyisocyanate compound (a)initially present in the mixture (M).

According to certain embodiments of the present invention, the aqueouspolyurethane dispersion further comprises other ingredients such asinorganic and organic pigments, dyes, leveling agents, viscosityregulators, natural and synthetic waxes, color transfer inhibitors,anti-foaming agents, matting agents, surfactants, detergents, opticalbrighteners. and the like. Said other ingredients are added in smallamounts, known to the skilled in the art, to provide specific propertiesto the aqueous polyurethane dispersion and/or the film and coatingsobtained thereof, such as notably mildew resistance, defoaming,defoaming, crosslinking for chemical resistance and heat resistance,flame retardancy, conductivity, light stability, and/or good flow andleveling during application.

The inventors have surprisingly found that the b-pyrrolidone basedaqueous polyurethane dispersion of the present invention has good wetdispersion properties such as viscosity, solids content, pH, appearance,heat age stability and is effective in providing smooth films havingimproved film properties, in particular dry film properties and coatingshaving improved properties such as increase in surface hardness asmeasured by Konig hardness, having improved mechanical properties, inparticular tensile strength and elongation and/or good water resistance.

In general, the aqueous polyurethane dispersion of the present inventionhas a total solids content from 10 to 75%, preferably from 20 to 65%,more preferably from 30 to 50% by weight.

It is further understood that the total solids content can be adjustedbased on the desired end use, for example the aqueous polyurethanedispersion can be diluted prior to final use.

The aqueous polyurethane dispersion of the present invention hasadvantageously a Brookfield viscosity less than 7000 mPA-s, preferablyless than 4000 mPA-s, more preferably less than 1000 mPA-s, as measuredat 25° C., 20 RPM using a Brookfield RV or RVT and a appropriatespindle.

Manufacturing of the Aqueous Polyurethane Dispersion

The aqueous polyurethane dispersion of the present invention can beprepared by a variety of methods known to the skilled person in the art.The manufacturing of the aqueous polyurethane dispersion is also anaspect of the present invention.

In one embodiment of the present invention, a method for themanufacturing of an aqueous polyurethane dispersion comprises thedispersing of the at least one isocyanate terminated polyurethaneprepolymer [prepolymer (P)], as defined above, in water.

In a preferred embodiment of the present invention, the prepolymer (P),as defined above, for use in the method for the preparation of theaqueous polyurethane dispersion is neutralized with the neutralizingagent, as detailed above, prior to dispersing in water.

As mentioned above, the compound (I) is preferably added afterdispersing the prepolymer (P) in water.

If desired, the prepolymer (P) may first react with the at least onecompound (I), as defined above, and/or the isocyanate monofunctionalreactive compound thereby forming a polyurethane polymer (polymer (PU))wherein said polymer (PU) is then dispersed in water.

In another embodiment of the present invention, a method for themanufacturing of an aqueous polyurethane dispersion comprises thedispersing of the polymer (PU), as defined above, in water.

Another aspect of the present invention is a process for the preparationof the prepolymer (P), as defined above, for use in the method for thepreparation of the aqueous polyurethane dispersion of the presentinvention, comprising reacting in the presence of the b-pyrrolidone, asdefined above, the mixture (M) which comprises:

-   -   (a) the at least one polyisocyanate compound (a), as defined        above,    -   (b) the at least one polyol compound (b), having a molecular        weight M_(w) of 200 to 8000 and a hydroxyl functionality of 1.5        to 6, as defined above,    -   (c) the at least one component (WD_(H)), as defined above which        comprises:        -   i. x mmol/kg of the at least one compound (WD_(HA)), as            defined above, and/or        -   ii. y mmol/kg of the at least one compound (WD_(HN)), as            defined above, and/or        -   iii. z mmol/kg of the at least one compound (WD_(HC)), as            defined above,        -   iv. w mmol/kg of the at least one compound (WD_(HZ)), as            defined above,        -   wherein

$\frac{{200x} + {70y} + {72z} + {75w}}{x + y + z + w} < {x + y + z + w} < \frac{{560x} + {248y} + {165z} + {300w}}{x + y + z + w}$

-   -   -   and x, y, z or w is different from 0 and all mmol/kg are            based on the weight of all the components initially present            in the mixture (M),

    -   (d) optionally, the at least one compound (I), as defined above,        and

    -   (e) optionally, the at least one isocyanate monofunctional        reactive compound, as defined above.

It is further understood that all definitions and preferences asdescribed above equally apply for this embodiment and all furtherembodiments, as described below.

The prepolymer (P) can be prepared by a variety of methods involvingintimate admixing of the constituent components of the mixture (M), asdefined above, with any optional component, as detailed above, in thepresence of the b-pyrrolidone, as defined above, for example by usingsuitable polymerization apparatus, including stirred tanks. Typically,the mixing of the polyisocyanate compound (a), as detailed above, thepolyol compound (b), as detailed above, the component (WD_(H)), asdetailed above, optionally, the compound (I), as detailed above,optionally, the isocyanate monofunctional reactive compound is carriedout in the presence of the b-pyrrolidone, as defined above, by usinglaboratory glassware with teflon mixing shaft, or, stainless steelcommercial reactor tanks with stainless steel mixing shafts and blades.

In general, the mixing of the constituent components of the mixture (M)with any optional component, as detailed above, in the presence of theb-pyrrolidone, as defined above, is carried out at reaction temperaturesranging from 20 to 180° C., preferably from 50 to 150° C.; morepreferably from 70 to 120° C.

It is further understood that the skilled person in the art will carryout said admixing according to general practice such as notably applyingoptimal time periods for addition and mixing in the presence of the theb-pyrrolidone, as defined above, the polyisocyanate compound (a), asdetailed above, the polyol compound (b), as detailed above, thecomponent (WD_(H)), as detailed above, optionally, the compound (I), asdetailed above, optionally, the isocyanate monofunctional reactivecompound, as detailed above.

In an advantageous embodiment of the present invention, the reaction ofthe polyisocyanate compound (a), as detailed above, with the polyolcompound (b), as detailed above, the component (WD_(H)), as detailedabove, optionally, the compound (I), as detailed above, and optionally,the isocyanate monofunctional reactive compound, as detailed above canbe accelerated by using conventional catalysts, commonly known by theskilled in the art in the polyurethane chemistry.

Non-limiting examples of suitable catalysts mention can notably be madeof compounds of divalent and tetravalent tin, more particularly thedicarboxylates of divalent tin and the dialkyl tin dicarboxylates ordialkoxylates, including notably dibutyl tin dilaurate, dibutyl tindiacetate, dioctyl tin diacetate, dibutyl tin maleate, tin(II) octoate,tin(II) phenolate or even the acetyl acetonates of divalent ortetravalent tin; the highly effective tertiary amines or amidines may beused as catalysts, optionally in combination with the tin compoundsmentioned above. Suitable tertiary amines can be both acyclic and, inparticular, cyclic compounds, including notably tetramethylbutanediamine, bis(dimethylaminoethyl)ether, 1,4-diazabicyclooctane(DABCO), 1,8-diazabicyclo-(5.4.0)-undecene, 2,2′-dimorpholinodiethylether or dimethyl piperazine or mixtures thereof; an organobismuthcatalyst such as the commercially available Coscat® 83 catalysts fromCasChem Company. Other commercially available bismuth catalysts areCoscat® 16, Coscat® 28, Coscat® Z-22 (CasChem Company).

Films (F) and Coatings (C)

The aqueous polyurethane dispersion of the present invention can thenadvantageously be further used to form (1) a film, (2) a coating or (3)to treat a substrate surface or at least part of a substrate surface.

Thus, another object of the invention is a method for manufacturing afilm [film (F), herein below] comprising using the aqueous polyurethanedispersion, as detailed above.

Yet another object of the invention is a method for manufacturing acoating [coating (C), herein below] comprising using the aqueouspolyurethane dispersion, as detailed above.

The inventors have surprisingly found that the b-pyrrolidone, as definedabove, already comprised in the aqueous polyurethane dispersion of thepresent invention acts as an excellent coalescing agent thereby aidingthe aqueous polyurethane dispersion in the formation of films (F) orcoatings (C) having a reduced tendency to tearing and/or forming holesand/or having improved surface appearance (e.g. having a lower amount ofsurface defects) and/or having an increased smoothness and/or havingimproved mechanical properties, in particular tensile strength andelongation and/or good water permeability.

According to certain embodiments, the b-pyrrolidone, as defined above,is additionally added to the aqueous polyurethane dispersion of thepresent invention after said aqueous polyurethane dispersion have beenprepared so as to achieve the desired coalescing in the formation offilms (F) or coatings (C).

However, the inventors have found that very reduced amounts of theb-pyrrolidone, as defined above, are only required to achieve thedesired coalescing of films (F) or coatings (C).

Techniques for manufacturing films and coatings are well known in theart. A typical method involves using a 10 wet mil gap under a solidsteel bar to spread the liquid dispersion uniformly across a flatsurface.

For the purpose of the present invention, the term “film (F)” possessesits usual meaning and is generally understood to encompass substantiallybi-dimensional sheets having thickness substantially lower than widthand length.

Thus another aspect of the present invention is a film (F) derived fromthe aqueous polyurethane dispersion, as detailed above.

In an advantageous embodiment of the present invention, the aqueouspolyurethane dispersion is applied to a surface or at least part of asubstrate surface thereby forming a coated surface.

Conventional coating techniques such as painting, spraying,flow-coating, transfer-coating, roller coating, brushing, dippingspreading, curtain coating and the like can be used.

Among suitable substrates mention may be made of wood, wood veneer,paper, paperboard, cardboard, textile, leather, nonwoven, surfaces ofplastics, glass, ceramic, mineral building materials and uncoated orcoated metals.

EXAMPLES

The invention will be now described in more detail with reference to thefollowing examples, whose purpose is merely illustrative and notintended to limit the scope of the invention.

The following abbreviations are used in the Examples:H12MDI: 4,4′-methylenebis(cyclohexyl isocyanate)IPDI: isophorone diisocyanatePiothane® 3000HA polyester: A polyester polyol obtained under the tradedesignation “Piothane® 3000HA” from Specialty Resin, A Division ofPanolam Industries International Inc.Piothane® 1000HA polyester: A polyester polyol obtained under the tradedesignation “Piothane® 1000HA” from Specialty Resin, A Division ofPanolam Industries International Inc.Piothane® 500BA polyester: A polyester polyol obtained under the tradedesignation “Piothane® 500BA” from Specialty Resin, A Division ofPanolam Industries International Inc.TMP: trimethylolpropaneCAPA™ 7203: A polycaprolactone/polycarbonate copolymer ester obtainedunder the trade designation “CAPA™ 7203” from Perstorp.DMPA: dimethylolpropionic acidYMER™ N120: A compounds (WD_(HN)) having the general formula (HN-1′) andn is 19 obtained under the trade designation “YMER™ N120” from Perstorp.DABCO® T-9: 1,4-Diazabicyclo[2.2.2]octane obtained under the tradedesignation “DABCO® T-9” from Air Products.DABCO® T-12: a dibutyl tin dilaurate catalyst obtained under the tradedesignation “DABCO® T-12” from Air Products.DEE FO® PI-40: A defoamer for aqueous systems obtained under the tradedesignation “DEE FO® PI-40” from Munzing Chemie GmbH.CosCat® 83: An organobismuth catalyst obtained under the tradedesignation “CosCat® 83” from CasChem Company.Metolat® 780 Ethylene Oxide: A surfactant obtained under the tradedesignation “Metolat® 780” from Munzing Chemie GmbH.TEA: trimethylamineBYK® 348 Flow aid: A polyether siloxane flow aid additive obtained underthe trade designation “BYK® 348” from BYK-Chemie USA.

Test Methods

Wet Dispersion Properties

The Wet Dispersion Properties are determined by measuring the Brookfieldviscosity, pH, total solids content, appearance, heat age stability,average particle size and coalescence.

The Brookfield viscosity: measurement of the Brookfield viscosity byusing a Brookfield RV or RVT, at 25° C., 20 RPM and using an appropriatespindle.

Coalescence: determination of coalescence is made by visual observationof the elimination of film ‘cracks’ and fractures upon air dry of a 254microns wet (10 wet mils) film on Lanetta cards at 50% relative humidityand 21.1° C. (70° F.) temperature.

Total solids content: determination by a thermogravimetric method usinga hot air forced convention oven at temperature of 150° C. anddetermining weight loss of wet dispersion samples when exposed for aduration of 2 hours.

Appearance: determination of appearance was made by visual observationof wet dispersion.

Heat Age Stability: The Heat Age Stability was carried out by exposureof the aqueous polyurethane dispersion to 49° C. in a sealed and tapedglass jar for 7 days.

Average particle size: The average particle size was measured by CPSdisc centrifugation analysis.

Air Dry Konig Hardness Development

The Air dry Konig hardness development was determined by applying 2coats of #52 rod deposition of each coating to steel Q-panels. Afterapplying the first coat, said first coat was dried for 30 minutes at anappropriate temperature. The second coat was then applied and dried at21° C. until 40% Relative Humidity. The Konig Hardness measurement wasrecorded in seconds for 1 to 5 days. After 5 days air drying, the panelswere reheated for 3 minutes at 150° C. After cooling to roomtemperature, the Konig Hardness was measured in seconds.

Water Resistance Properties

The water spot resistance was determined by applying a 254 microns wet(10 wet mils) deposition on Lanetta cards by using Byrd Bars which werethen dried at 21° C. until 40% Relative Humidity for about 24 hours.Water soaked balls were the applied to said film surfaces covered withglass jar.

Dry Film Properties

The dry film properties were determined by applying a 254 microns wet(10 wet mils) coating onto a mylar film by using Byrd Bars. The coatedfilms were air dried overnight. The coated films were then further ovendried at 150° C. during 3 minutes. Modulus, Tensile at Break, UltimateElongation using Shimadzo Tensile test machine (Crosshead Speed=0.4inches/min; Jaw Separation=3 inches, Sample width=1 inch) were recordedaccording to ASTM D2370-98 Standard Test Method for tensile propertiesof organic coatings

Aqueous Polyurethane Dispersion Systems Including Anionic HydrophilicGroup or Potentially Anionic Hydrophilic Groups [Compound (WD_(HA))]

Example 1 (E1)

Components initially present in the mixture (M) of example 1:

-   -   62.32 g of H12MDI (0.475 equivalents)    -   251.01 g of Piothane® 3000HA polyester (0.158 equivalents)    -   10.63 g of DMPA (0.158 equivalents or 245 mmol/kg based on the        weight of H12MDI, Piothane® 3000HA polyester and DMPA).

To a reactor tank with stainless steel mixing shafts and blades, 62.32 gof H12MDI, 251.01 g of Piothane® 3000HA polyester, 10.63 g of DMPA and57.17 g of N-n-butylpyrrolidone were added. Start mixing, heat themixture to 80° C. and add 0.030 g DABCO® T-9 Stannous Octoate catalyst.The reaction was reacted to a residual polyisocyanate content (i.e. NCOgroup content) of 1.70%. The reaction mixture (prepolymer (P)) wascooled until 78° C. and the Brookfield viscosity was measured at 25° C.,20 RPM and a #4 Spindle (see Table 1). To the reaction mixture at 78° C.was added 7.94 g of TEA neutralizing agent. To a separate dispersionkettle, 454.91 g of water at 23-24° C. and 0.16 g of DEE FO® PI-40defoamer were added and agitated. 329.67 g of the reaction mixture (i.e.the prepolymer (P) with TEA) was added to the water in the separatedispersion tank, allowing incorporation and dispersion of the reactionmixture into the water over a 7 minutes period.

The reaction mixture dispersed easily. It started opaque white andcleared to semi-trans/opaque.

To the dispersion was added 5.50 g of 64% hydrazine hydrate diluted withwater to 35% hydrazine content. Mixed for 4 minutes after addition ofthe hydrazine hydrate.

The resulting dispersion has a polyurethane solids content of 35.28% byweight. The resulting dispersion has been subjected to the followingtest methods which are described in detail above: Wet DispersionProperties test (i.e. Viscosity, total solids content, average particlesize, pH, appearance, heat age stability and coalescence); the air dryKonig hardness development test, water resistance property test and dryfilm property test. The results are summarized in Table 1.

Comparative Example 2 (CE2)

Comparative example 2 was prepared in the same way as in Example 1,except that 57.17 g of N-methylpyrrolidone (NMP) was added instead of57.17 g of N-n-butylpyrrolidone, the reaction was reacted to a residualpolyisocyanate content (i.e. NCO group content) of 1.68% and to thedispersion was added 5.43 g of 64% hydrazine hydrate diluted with waterto 35% hydrazine content.

The reaction mixture dispersed with great difficulty, became Flocculantupon entering water, very slow feed was required. The resultingdispersion was Opaque white with flocculant

The resulting dispersion has a polyurethane solids content of 35.49% byweight. The resulting dispersion has been subjected to the followingtest methods which are described in detail above: Wet DispersionProperties test (i.e. Viscosity, total solids content, average particlesize, pH, appearance, heat age stability and coalescence); the air dryKonig hardness development test, water resistance property test and thedry film property test. The results are summarized in Table 1.

Example 3 (E3)

Components initially present in the mixture (M) of example 3:

-   -   155.39 g of H12MDI (1.185 equivalents)    -   190.66 g of Piothane®1000HA polyester (0.385 equivalents)    -   13.92 g of DMPA (0.207 equivalents or 288 mmol/kg based on the        weight of H12MDI, Piothane® 3000HA polyester and DMPA).

To a reactor tank with stainless steel mixing shafts and blades, 155.39g of H12MDI, 190.66 g of Piothane® 1000HA polyester, 13.92 g of DMPA and40.00 g of N-n-butylpyrrolidone were added. Start mixing, heat themixture to 80° C. and add 0.036 g DABCO® T-9 Stannous Octoate catalyst.The reaction mixture was reacted to a residual polyisocyanate content(i.e. NCO group content) of 6.07%. The reaction mixture (prepolymer (P))was cooled until 77° C. and the Brookfield viscosity was measured at 25°C., 20 RPM and a #4 Spindle (see Table 1). To the reaction mixture at77° C. was added 10.31 g of TEA neutralizing agent. To a separatedispersion kettle, 528.66 g of water at 23-24° C., 0.17 g of DEE FO®PI-40 defoamer and 1.79 g of Metolat® 780 Ethylene Oxide were added andagitated. 348.76 g of the reaction mixture (i.e. the prepolymer (P) withTEA) was added to the water in the separate dispersion kettle, allowingincorporation and dispersion of the reaction mixture into the water overa 4 minute period. The dispersion was mixed for 39 minutes aftercomplete addition of said reaction mixture. To the dispersion was added20.67 g of 64% hydrazine hydrate diluted with water to 35% hydrazinecontent and the dispersion was mixed for 8 minutes after addition of thehydrazine hydrate. The resulting dispersion has a polyurethane solidscontent of 38.18% by weight. The resulting dispersion has been subjectedto the following test methods which are described in detail above: WetDispersion Properties test (i.e. Viscosity, total solids content,average particle size, pH, appearance, heat age stability andcoalescence); the air dry Konig hardness development test, waterresistance property test. The results are summarized in Table 1.

Comparative Example 4 (CE4)

Comparative example 4 was prepared in the same way as in Example 3,except that 40 g of N-methylpyrrolidone (NMP) was added instead of 40 gof N-n-butylpyrrolidone, the reaction was reacted to a residualpolyisocyanate content (i.e. NCO group content) of 6.18% and to thedispersion was added 20.59 g of 64% hydrazine hydrate diluted with waterto 35% hydrazine content. The resulting dispersion has a polyurethanesolids content of 36.37% by weight. The resulting dispersion has beensubjected to the following test methods which are described in detailabove: Wet Dispersion Properties test (i.e. Viscosity, total solidscontent, average particle size, pH, appearance, heat age stability andcoalescence); the air dry Konig hardness development test and the waterresistance property test. The results are summarized in Table 1.

Example 5 (E5)

Components initially present in the mixture (M) of example 5:

-   -   180.00 g of H12MDI (1.372 equivalents)    -   142.63 g of Piothane® 500BA polyester (0.541 equivalents)    -   1.08 g of TMP (0.024 equivalents)    -   16.25 g of DMPA (0.240 equivalents or 357 mmol/kg based on the        weight of H12MDI, Piothane® 500BA polyester, TMP and DMPA).

To a reactor tank with stainless steel mixing shafts and blades, 180.00g of H12MDI, 142.63 g of Piothane® 500BA polyester, 1.08 g TMP and 60.00g of N-n-butylpyrrolidone were added. Start mixing, heat the mixture to80° C. and add 0.033 g CosCat® Bismuth catalyst. The reaction mixturewas reacted to a residual polyisocyanate content (i.e. NCO groupcontent) of 8.31%. The reaction mixture was cooled until 95° C. and16.25 g of DMPA was added. The reaction mixture was further reacted to aresidual polyisocyanate content (i.e. NCO group content) of 5.68%. Thereaction mixture (prepolymer (P)) was cooled until 77° C. and theBrookfield viscosity was measured at 25° C., 20 RPM and a #4 Spindle(see Table 1). To the reaction mixture at 77° C. was added 11.98 g ofTEA neutralizing agent. To a separate dispersion kettle, 511.08 g ofwater at 23-24° C. and 0.17 g of DEE FO® PI-40 defoamer were added andagitated. 339.89 g of the reaction mixture (i.e. the prepolymer (P) withTEA) was added to the water in the separate dispersion kettle, allowingincorporation and dispersion of the reaction mixture into the water overa 13 minute period. The dispersion was mixed for 64 minutes aftercomplete addition of said reaction mixture. To the dispersion was added18.77 g of 64% hydrazine hydrate diluted with water to 35% hydrazinecontent and was mixed for 10 minutes after addition of the hydrazinehydrate. The resulting dispersion has a polyurethane solids content of36.81% by weight. The resulting dispersion has been subjected to the WetDispersion Properties test (i.e. Viscosity, total solids content, pH,appearance, and coalescence), as described in detail above. The resultsare summarized in Table 1. The resulting dispersion had poor coalescenceat room temperature, showing that not enough N-n-butylpyrrolidone wasadded.

Single Co-Solvent Coalescence—Example 5a (E5a)

To the resulting dispersion system (826.09 g), as obtained in example 5,95.38 g of water was added to obtain a polyurethane solids content of33.00% by weight (PUD-5). The Brookfield viscosity, as measured at 25°C., 20 RPM and a #2 Spindle was 110 mPA-s.

To 100 g of this polyurethane dispersion system (PUD-5) at 33.00% solidscontent, only 1.75 g of N-n-butylpyrrolidone and 0.50 g of BYK® 348 Flowaid were added in order to achieve coalescence from a 254 microns wet(10 wet mils) film applied to Lanetta cards air dried at 23° C. (seeresults Table 2). The Konig hardness was now determined by applying a177.8 microns wet (7 wet mils) of coalesced coating to steel Q-panels byusing a Byrd Bar. The Konig Hardness measurement was recorded in secondsfor 1 to 6 days. After 6 days air drying, the panels were reheated in anoven for 5 minutes at 150° C. (see results Table 2). The wet film drytime property was determined by applying a 152.4 microns wet (6 wetmils) coating onto a mylar film by using Byrd Bars at 22° C. and at30-40% Relative Humidity. The Gardner dry time was measured (see resultsTable 2).

Dual Co-Solvent Coalescence—Example 5b (E5b)

To the resulting dispersion system (826.09 g), as obtained in example 5,95.38 g of water was added to obtain a polyurethane solids content of33.00% by weight (PUD-5). The Brookfield viscosity, as measured at 25°C., 20 RPM and a #2 Spindle was 110 mPA-s.

To 100 g of the polyurethane dispersion system at 33.00% solids content(PUD-5), 3 g of dipropylene glycol dimethyl ether, 3 g ofN-n-butylpyrrolidone and 0.53 g of BYK® 348 Flow aid were added. TheKonig hardness was now determined by applying a 177.8 microns wet (7 wetmils) of coalesced coating to steel Q-panels by using a Byrd Bar. TheKonig Hardness measurement was recorded in seconds for 1 to 6 days.After 6 days air drying, the panels were reheated in an oven for 5minutes at 150° C. (see results Table 2). The wet film dry time propertywas determined by applying a 152.4 microns wet (6 wet mils) coating ontoa mylar film by using Byrd Bars at 22° C. and at 30-40% RelativeHumidity. The Gardner dry time was measured (see results Table 2).

Comparative Example 6 (CE6)

Comparative example 6 was prepared in the same way as in Example 5,except that 60 g of N-methylpyrrolidone (NMP) was added instead of 60 gof N-n-butylpyrrolidone, the reaction was reacted to a first residualpolyisocyanate content (i.e. NCO group content) of 8.59% and to a finalresidual polyisocyanate content after the DMPA was added of 5.91%, andto the dispersion was added 19.53 g of 64% hydrazine hydrate dilutedwith water to 35% hydrazine content. The resulting dispersion has apolyurethane solids content of 35.62% by weight. The resultingdispersion has been subjected to the Wet Dispersion Properties test(i.e. Viscosity, total solids content, pH, appearance, and coalescence),as described in detail above. The results are summarized in Table 1. Theresulting dispersion had also a poor coalescence at room temperature,showing that not enough NMP was added.

Single Co-Solvent Coalescence—Comparative Example 6a (CE 6a)

To the resulting dispersion system (830.60 g), as obtained incomparative example 6, 65.94 g of water was added to obtain apolyurethane solids content of 33.00% by weight (PUD-C6). The Brookfieldviscosity, as measured at 25° C., 20 RPM and a #2 Spindle was 40 mPA-s.

To 100 g of this polyurethane dispersion system at 33.00% solids content(PUD-C6), 6.00 g of NMP and 0.50 g of BYK® 348 Flow aid was necessary toadd in order to achieve coalescence from a 254 microns wet (10 wet mils)film applied to Lanetta cards air dried at 23° C. (see results Table 2).The Konig hardness was now determined by applying a 177.8 microns wet (7wet mils) of coalesced coating to steel Q-panels by using a Byrd Bar.The Konig Hardness measurement was recorded in seconds for 1 to 6 days.After 6 days air drying, the panels were reheated in an oven for 5minutes at 150° C. (see results Table 2). The wet film dry time propertywas determined by applying a 152.4 microns wet (6 wet mils) coating ontoa mylar film by using Byrd Bars at 22° C. at a 30-40% Relative Humidity.The Gardner dry time was measured (see results Table 2).

Dual Co-Solvent Coalescence—Comparative Example 6b (CE6b)

To the resulting dispersion system (830.60 g), as obtained incomparative example 6, 65.94 g of water was added to obtain apolyurethane solids content of 33.00% by weight (PUD-C6). The Brookfieldviscosity, as measured at 25° C., 20 RPM and a #2 Spindle was 40 mPA-s.

To 100 g of this polyurethane dispersion system at 33.00% solids content(PUD-C6), 3 g of dipropylene glycol dimethyl ether, 3 g of NMP and 0.53g of BYK® 348 Flow aid were added. The Konig hardness was now determinedby applying a 177.8 microns wet (7 wet mils) of coalesced coating tosteel Q-panels by using a Byrd Bar. The Konig Hardness measurement wasrecorded in seconds for 1 to 6 days. After 6 days air drying, the panelswere reheated in an oven for 5 minutes at 150° C. (see results Table 2).The dry film property was determined by applying a 152.4 microns wet (6wet mils) coating onto a mylar film by using Byrd Bars at 22° C. until30-40% Relative Humidity was reached. The Gardner dry time was measured(see results Table 2).

Comparative Example 7 (CE7)

Comparative example 6 was prepared in the same way as in Example 5,except that 60 g of N-ethylpyrrolidone (NEP) was added instead of 60 gof N-n-butylpyrrolidone, the reaction was reacted to a first residualpolyisocyanate content (i.e. NCO group content) of 8.62% and and to afinal residual polyisocyanate content of 5.69% after the DMPA was addedand to the dispersion was added 19.53 g of 64% hydrazine hydrate dilutedwith water to 35% hydrazine content. The resulting dispersion has apolyurethane solids content of 35.90% by weight. The resultingdispersion has been subjected to the Wet Dispersion Properties test(i.e. Viscosity, total solids content, pH, appearance, and coalescence),as described in detail above. The results are summarized in Table 1. Theresulting dispersion had also a poor coalescence at room temperature,showing that not enough NEP was added.

Single Co-Solvent Coalescence—Comparative Example 7a (CE7a)

To the resulting dispersion system (830.60 g), as obtained incomparative example 7, 65.94 g of water was added to obtain apolyurethane solids content of 33.00% by weight (PUD-C7). The Brookfieldviscosity, as measured at 25° C., 20 RPM and a #2 Spindle was 60 mPA-s.

To 100 g of this polyurethane dispersion system at 33.00% solids content(PUD-C7), 7.00 g of NEP and 0.50 g of BYK® 348 Flow aid was necessary toadd in order to achieve coalescence from a 254 microns wet (10 wet mils)film applied to Lanetta cards air dried at 23° C. (see results Table 2).The Konig hardness was now determined by applying a 177.8 microns wet (7wet mils) of coalesced coating to steel Q-panels by using a Byrd Bar.The Konig Hardness measurement was recorded in seconds for 1 to 6 days.After 6 days air drying, the panels were reheated in an oven for 5minutes at 150° C. (see results Table 2). The wet film dry time propertywas determined by applying a 152.4 microns wet (6 wet mils) coating ontoa mylar film by using Byrd Bars at 22° C. and at 30-40% RelativeHumidity. The Gardner dry time was measured (see results Table 2).

Dual Co-Solvent Coalescence—Comparative Example 7b (CE7b)

To the resulting dispersion system (830.60 g), as obtained incomparative example 7, 65.94 g of water was added to obtain apolyurethane solids content of 33.00% by weight (PUD-C7). The Brookfieldviscosity, as measured at 25° C., 20 RPM and a #2 Spindle was 40 mPA-s.

To 100 g of this polyurethane dispersion system at 33.00% solids content(PUD-C7), 3 g of dipropylene glycol dimethyl ether, 3 g of NEP and 0.53g of BYK® 348 Flow aid were added. The Konig hardness was now determinedby applying a 177.8 microns wet (7 wet mils) of coalesced coating tosteel Q-panels by using a Byrd Bar. The Konig Hardness measurement wasrecorded in seconds for 1 to 6 days. After 6 days air drying, the panelswere reheated in an oven for 5 minutes at 150° C. (see results Table 2).The dry film property was determined by applying a 152.4 microns wet (6wet mils) coating onto a mylar film by using Byrd Bars at 22° C. until30-40% Relative Humidity was reached. The Gardner dry time was measured(see results Table 2).

Example 8 (E8)

Components initially present in the mixture (M) of example 8:

-   -   88.63 g of H12MDI (0.676 equivalents)    -   214.18 g of Piothane® 3000HA polyester (0.135 equivalents)    -   21.16 g of DMPA (0.315 equivalents or 486 mmol/kg based on the        weight of H12MDI, Piothane® 3000HA polyester and DMPA).

To a reactor tank with stainless steel mixing shafts and blades, 88.63 gof H12MDI, 214.18 g of Piothane® 3000HA polyester, 21.16 g of DMPA and81.00 g of N-n-butylpyrrolidone were added. Start mixing, heat themixture to 80° C. and add 0.032 g DABCO® T-9 Stannous Octoate catalyst.The reaction mixture was reacted to a residual polyisocyanate content(i.e. NCO group content) of 2.25%. The reaction mixture (prepolymer (P))was cooled until 87° C. and the Brookfield viscosity was measured at 25°C., 20 RPM and a #4 Spindle (see Table 1). To a separate dispersionkettle, 413.12 g of water at 23-24° C., 11.44 g of dimethylethanol amineneutralizing agent, 0.15 g of DEE FO® PI-40 defoamer were added andagitated. 330 g of the reaction mixture (i.e. the prepolymer (P) wasadded to the water in the separate dispersion kettle, allowingincorporation and dispersion of the reaction mixture into the water overa 7 minute period. The dispersion was mixed for 33 minutes aftercomplete addition of said reaction mixture. To the dispersion was added7.44 g of 64% hydrazine hydrate diluted with water to 35% hydrazinecontent and was mixed for 10 minutes after addition of the hydrazinehydrate. The resulting dispersion has a polyurethane solids content of37.49% by weight. The resulting dispersion has been subjected to thefollowing test methods which are described in detail above: WetDispersion Properties test (i.e. Viscosity, total solids content,average particle size, pH, appearance, heat age stability andcoalescence); the air dry Konig hardness development test, waterresistance property test and the dry film property test. The results aresummarized in Table 1.

Due to the high BKFLD viscosity of 7000 mPA-s, as illustrated in Table1, 100 g of the resulting dispersion having a polyurethane solidscontent of 37.49% by weight was further diluted with 9.37 g water untilreflow characteristics were obtained. The air dry Konig hardnessdevelopment test was again measured and results are shown in Table 1.

Comparative Example 9 (CE9)

Comparative example 9 was prepared in the same way as in Example 8,except that 81 g of N-methylpyrrolidone (NMP) was added instead of 81 gof N-n-butylpyrrolidone (n-NBP), the reaction was reacted to a residualpolyisocyanate content (i.e. NCO group content) of 2.20% and to thedispersion was added 7.28 g of 64% hydrazine hydrate diluted with waterto 35% hydrazine content. The resulting dispersion has a polyurethanesolids content of 36.72% by weight. The resulting dispersion has beensubjected to the following test methods which are described in detailabove: Wet Dispersion Properties test (i.e. Viscosity, total solidscontent, average particle size, pH, appearance, heat age stability andcoalescence); the air dry Konig hardness development test, waterresistance property test and the dry film property test. The results aresummarized in Table 1.

Due to the high BKFLD viscosity of 710 mPA-s, as illustrated in Table 1,100 g of the resulting dispersion having a polyurethane solids contentof 36.72% by weight was further diluted with 9.37 g water until reflowcharacteristics were obtained. The air dry Konig hardness developmenttest was again measured and results are shown in Table 1.

TABLE 1 Characteristics of the aqueous polyurethane dispersion ofexamples 1, 3, 5, 8 and the comparative examples 2, 4, 6, 7 and 9 #EXAMPLE E1 CE2 E3 CE4 E5 CE6 CE7 E8 CE9 CO-SOLVENT n-NBP NMP n-NBP NMPn-NBP NMP NEP n-NBP NMP Amount DMPA (x mmol/kg) 245 245 288 288 357 357357 486 486 Wet Dispersion Properties^(a) Total Solids Content 35.28%35.49% 37.18% 36.37% 36.81% 35.62% 35.90% 37.49% 36.72% Appearanceopaque/ opaque/white translucent opaque/ semi- semi- semi- clear/translucent semi- sediment semi- translucent translucent translucenttranslucent translucent translucent pH 7.98 7.99    7.98    8.03 8.568.59 8.53    8.29    8.27 Coalescense excellent excellent excellentborderline/ poor poor poor excellent excellent some mudcracks Heat AgeStability clean heavy clean/ opaque/ — — — clean/ clean/ sedimentation/translucent semi- clear translucent separation translucent BKFLDviscosity (mPA-s) 400 380 330  40 4000 70 260 7000  710 Average particlesize (μm) 0.045 0.081 — — 0.034 0.031 0.029 — — Air dry Konig hardnessdevelopment^(b) 1 day air dry 69 sec 64 sec 66 sec 74 sec NA NA NA 69sec 64 sec 2 day air dry 76 sec 85 sec 66 sec 74 sec NA NA NA 76 sec 85sec 3 day air dry 82 sec 88 sec 68 sec 76 sec NA NA NA 82 sec 88 sec 4day air dry 91 sec 86 sec 75 sec 75 sec NA NA NA 91 sec 86 sec 5 day airdry 93 sec 89 sec 76 sec 76 sec NA NA NA 93 sec 89 sec Oven dry 3minutes @ 45 sec 54 sec 59 sec 60 sec NA NA NA 45 sec 54 sec 150° C.Water resistance properties^(c) 1 hour water soak No affect No affect Noaffect No affect NA NA NA No affect No affect 24 hour water soak Noaffect No affect No affect No affect NA NA NA No affect No affect Dryfilm properties^(d) Elongation modulus 100% 1243 psi 1144 psi — — NA NANA 1963 psi 1690 psi Elongation modulus 100% 1365 psi 1242 psi — — NA NANA 2269 psi 2262 psi Elongation modulus 100% 1606 psi 1572 psi — — NA NANA 2694 psi 2907 psi Tensile at break 2527 psi 1709 psi — NA NA NA 3028psi 3950 psi Ultimate Elongation   565%   465% NA NA NA   514%   643%^(a,b,c,d)the test methods are explained in detail above; NA means notapplicable

TABLE 2 Characteristics of the aqueous polyurethane dispersion ofexamples 5a and 5b and the comparative examples 6a, 6b, 7a and 7b. #EXAMPLE E5a CE6a CE7a PUD-5 (parts) 100 PUD-C6 (parts) 100 PUD-C7(parts) 100 BYK ® 348 Flow aid (parts) 0.50 0.50 0.50 n-BNP (parts) 1.75NMP (parts) 6.00 NEP (parts) 7.00 Total solvent required for 7.44 11.6912.69 coalescence (parts) Total solvent as % of PUD 23.05% 37.73% 41.34%solids Air dry Konig hardness development: 7 wet mils film applied viaByrd Bar to Steel Q-Panels. 1 day air dry 33 sec 39 sec 58 sec 2 day airdry 53 sec 61 sec 79 sec 3 day air dry 65 sec 73 sec 88 sec 4 day airdry 82 sec 87 sec 99 sec 5 day air dry 87 sec 90 sec 105 sec 6 day airdry 88 sec 89 sec 113 sec Oven dry 3 minutes @ 150° C. 116 sec 109 sec119 sec Gardner dry time: 6 wet mils coated to Mylar film. Dry to touch8 min 38 min 35 min Dust free 27 min 58 min 60 min Dry through 28 min 66min 70 min # Example E5b CE6b CE7b PUD-5 (parts) 100 PUD-C6 (parts) 100PUD-C7 (parts) 100 BYK ® 348 Flow aid (parts) 0.53 0.53 0.53 n-BNP(parts) 3.00 NMP (parts) 3.00 NEP (parts) 3.00 dipropylene glycoldimethyl 3.00 3.00 3.00 ether (parts) Coalescense Excellent AcceptableAcceptable - mud cracking in high spots Air dry Konig hardnessdevelopment: 7 wet mils film applied via Byrd Bar to Steel Q-Panels. 1day air dry 37 sec 47 sec 67 sec 2 day air dry 62 sec 68 sec 87 sec 3day air dry 75 sec 79 sec 96 sec 4 day air dry 90 sec 91 sec 105 sec 5day air dry 96 sec 94 sec 105 sec 6 day air dry 98 sec 92 sec 102 secOven dry 3 minutes @ 150° C. 119 sec 108 sec 122 sec Gardner dry time: 6wet mils coated to Mylar film. Dry to touch 12 min 17 min 20 min Dustfree 48 min 49 min 47 min Dry through 52 min 53 min 53 min

The results, as summarized in Table 1, clearly demonstrate thatpolyurethane prepolymers using N-n-butylpyrrolidone (n-NBP) as thedispersion solvent can be made at lower levels of DMPA compared to thoseusing NMP as the dispersion solvent. In particular, in example 1, then-NBP-based polyurethane prepolymer (P) incorporating a low DMPA levelof 245 mmol/kg was easy to disperse and showed a clean, semi-translucentappearance. On the contrary, in comparative example 2, the NMP-basedpolyurethane prepolymer (P) incorporating said low DMPA level of 245mmol/kg was more difficult to disperse and showed heavy flocculation.

In spite of the extremely high viscosity of the prepolymer (P), theN-n-butylpyrrolidone co-solvent demonstrated excellent solubilizingeffect of the prepolymer (P) solids and allowed easy flow andincorporation of the hydrophobic prepolymer into the water phase.

The results as shown in Table 1 and Table 2 also demonstrates thatN-n-butylpyrrolidone (n-NBP) offers significantly improved coalescenceof n-NBP-based polyurethane dispersion films, and this can enablesignificant VOC reduction due to the lower co-solvent demand for arequired degree of coalescence.

With reference to example E5b in Table 2, the Inventors especially notethat even when equal levels of n-NBP, as compared to NMP or NEP, areused, the n-NBP-based polyurethane dispersion systems still exhibit morerapid comparative touch dry times with exceptional solvency and improvedfilm formation.

Aqueous Polyurethane Dispersion Systems Including Potentially AnionicHydrophilic Groups and Non-Ionic Hydrophilic Groups

Example 10 (E10)

Components initially present in the mixture (M) of example 10:

-   -   58.45 g of IPDI (0.526 equivalents)    -   226.88 g of CAPA™ 7203 polycaprolactone/polycarbonate copolymer        ester (0.223 equivalents)    -   32.49 g of YMER™ N120 (0.064 equivalents or 100 mmol/kg based on        the weight of H12MDI, YMER™ N120, CAPA™ 7203 copolymer ester and        DMPA)    -   2.14 g of DMPA (0.032 equivalents) or 50 mmol/kg based on the        weight of H12MDI, YMER™ N120, CAPA™ 7203 copolymer ester and        DMPA).

To a reactor tank with stainless steel mixing shafts and blades, 58.45 gof IPDI, 226.88 g of CAPA™ 7203 copolymer ester, 32.49 g of YMER™ N120,2.14 g of DMPA and 80.00 g of N-n-butylpyrrolidone were added. Startmixing, heat the mixture to 88-92° C. and add 0.03 g DABCO® T-12 DibutylTin dilaurate catalyst. The reaction was reacted to a residualpolyisocyanate content (i.e. NCO group content) of 2.11%. The reactionmixture (prepolymer (P)) was cooled until 74° C. and the Brookfieldviscosity was measured at 25° C., 10 RPM and a #6 Spindle (see Table 3).To a separate dispersion kettle, 424.39 g of water at 22-23° C. and 0.15g of DEE FO® PI-40 defoamer were added and agitated. 330.00 g of thereaction mixture (i.e. the prepolymer (P)) was added to the water in theseparate dispersion tank, allowing incorporation and dispersion of thereaction mixture into the water over a 6 minute period. The dispersionwas mixed for 19 minutes after complete addition of said reactionmixture. To the dispersion was added 0.87 g of diethylenetriamine, 3.73g of ethylenediamine and 8.51 g water. The resulting dispersion has apolyurethane solids content of 35.00% by weight. The resultingdispersion has been subjected to the following test methods which aredescribed in detail above: Wet Dispersion Properties test (i.e.Viscosity, total solids content, average particle size, pH, appearance,heat age stability and coalescence); and dry film property test. Thewater spot resistance was determined by applying a 152.4 microns wet (6wet mils) deposition on Lanetta cards by using Byrd Bars which were thendried at 21° C. until 30% Relative Humidity for about 12 hours. Thewater spot resistance was determined by application of water direct tothe dried coating. The results are summarized in Table 3.

Comparative Example 11 (CE11)

Comparative example 11 was prepared in the same way as in Example 10,except that 80.00 g of N-methylpyrrolidone (NMP) was added instead of80.00 g of N-n-butylpyrrolidone, the reaction was reacted to a residualpolyisocyanate content (i.e. NCO group content) of 2.14% and was added0.87 g of diethylenetriamine, 3.78 g of ethylenediamine and 8.63 gwater. A coagulated gel was obtained.

Comparative Example 12 (CE12)

Comparative example 12 was prepared in the same way as in Example 10,except that 80.00 g of N-ethylpyrrolidone (NEP) was added instead of80.00 g of N-n-butylpyrrolidone, the reaction was reacted to a residualpolyisocyanate content (i.e. NCO group content) of 2.14% and was added0.87 g of diethylenetriamine, 3.78 g of ethylenediamine and 8.63 gwater. A coagulated gel was obtained.

TABLE 3 Characteristics of the aqueous polyurethane dispersion ofexample 10 (E10) and comparative examples 11 (CE11) and 12 (CE12). #Example E10 CE11 CE12 Co-solvent n-NBP NMP NEP Amount DMPA (x mmol/kg)50  50  50 Amount YMER ™ N120 (y 100 100 100 mmol/kg) Wet DispersionProperties Total Solids Content 35.89% 35.00% 35.00% Appearanceopaque/white coagulated coagulated liquid gel gel pH 6.57 NA NACoalescense excellent NA NA Heat Age Stability clean coagulatedcoagulated gel gel BKFLD viscosity (mPA-s) 40 solid solid Dry filmproperties Elongation modulus 100% 150 psi NA NA Elongation modulus 100%350 psi NA NA Elongation modulus 100% 780 psi NA NA Tensile at break5200 psi NA NA Ultimate Elongation  1200% NA NA Water Spot Resistancetest 30 min exposure No effect NA NA 24 hour exposure under Slight blushNA NA cover with full recovery NA means not applicable

Table 3 clearly demonstrates that the N-n-butylpyrrolidone significantlyassists the dispersion of polyurethane entities into a water phase in amanner far superior to the more traditional co-solvents commonly used,and, allows for the creation of stable, usable polyurethane dispersionsat hydrophilic entity levels below that which are allowed for the morecommonly used co-solvents.

1. An aqueous polyurethane dispersion comprising: A. at least oneisocyanate terminated polyurethane prepolymer [prepolymer (P), hereinafter] prepared by reacting in the presence of at least one pyrrolidone[(b-pyrrolidone, herein after] selected from the group consisting ofN-n-butylpyrrolidone, N-isobutylpyrrolidone, N-sec-butylpyrrolidone andN-tert-butylpyrrolidone, a mixture (M) which comprises: (a) at least onepolyisocyanate compound (a), (b) at least one polyol compound (b),having a molecular weight M_(w) of 200 to 8000 and a hydroxylfunctionality of 1.5 to 6, (c) at least one water dispersible enhancingcomponent having at least one hydrophilic group or potentiallyhydrophilic group [component (WD_(H)), herein after] and comprising: i.x mmol/kg of at least one water dispersible enhancing compound having atleast one anionic hydrophilic group or potentially anionic hydrophilicgroup [compound (WD_(HA)), herein after], and/or ii. y mmol/kg of atleast one water dispersible enhancing compound having at least onenon-ionic hydrophilic group or potentially non-ionic hydrophilic group[compound (WD_(HN)) herein after], and/or iii. z mmol/kg of at least onewater dispersible enhancing compound having at least one cationichydrophilic group or potentially cationic hydrophilic group [compound(WD_(HC)), herein after], iv. w mmol/kg of at least one waterdispersible enhancing compound having at least one zwitterionichydrophilic group or potentially zwitterionic hydrophilic group[compound (WD_(HZ)), herein after], wherein$\frac{{200x} + {70y} + {72z} + {75w}}{x + y + z + w} < {x + y + z + w} < \frac{{560x} + {248y} + {165z} + {300w}}{x + y + z + w}$and at least one of x, y, z or w is different from 0 and all mmol/kg arebased on the weight of all the components initially present in themixture (M), B. optionally, at least one isocyanate-reactive compound[compound (I)] herein after], different from the polyol compound (b) anddifferent from the component (WD_(H)), having reactive groups chosenamong alcoholic hydroxyl groups or primary or secondary amino group; andC. water.
 2. The aqueous polyurethane dispersion according to claim 1wherein the b-pyrrolidone is N-n-butylpyrrolidone.
 3. The aqueouspolyurethane dispersion according to claim 1 or claim 2 wherein theweight percent (wt. %) of the b-pyrrolidone, relative to the totalweight of all the components initially present in the mixture (M) isless than 50 wt. %.
 4. The aqueous polyurethane dispersion according toclaim 1, wherein the polyisocyanate compound (a) is chosen fromaliphatic, cycloaliphatic, araliphatic and aromatic diisocyanates andpolyisocyanates.
 5. The aqueous polyurethane dispersion according toclaim 1, wherein the compound (WD_(HA)) is chosen from compounds havingthe general formula (HA):FG-R¹-AG  formula (HA) wherein FG is at least one functional group,wherein said functional group is selected from the group consisting of—OH, —SH, —NH₂ and —NHR², wherein R² is an alkyl or aryl group, R² isselected from the group consisting of methyl, ethyl, isopropyl,n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopentyl orcyclohexyl, R¹ is an aliphatic, cycloaliphatic or aromatic radicalcontaining 1 to 20 carbon atoms, and AG is at least one anionic orpotential anionic group wherein said anionic or potential anionic groupis selected from the group consisting of —COOY, —SO₃Y and —PO(OY)₂wherein each of Y, equal to or different from each other, is selectedfrom the group consisting of hydrogen, ammonium salt, alkali metal, andalkaline earth metal.
 6. The aqueous polyurethane dispersion accordingto claim 1, wherein compounds (WD_(HN)) is chosen from compounds havingthe general formula (HN):FG-R¹—Z—X—R′  formula (HN) wherein FG is at least one functional group,wherein said functional group is selected from the group consisting of—OH, —SH, —NH₂ and —NHR², wherein R² is an alkyl or aryl group, R² isselected from the group consisting of methyl, ethyl, isopropyl,n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopentyl andcyclohexyl, R¹ is an aliphatic, cycloaliphatic or aromatic radicalcontaining 1 to 20 carbon atoms, X is a polyalkylene oxide chain having5 to 100 repeating alkylene oxide units, which may be composed to anextent of at least 40% of repeating ethylene oxide units and which inaddition to said repeating ethylene oxide units may be composed ofpropylene oxide, butylene oxide or styrene oxide units, Z is oxygen or—NR⁶—, wherein R⁶ is H, an alkyl or aryl group, R⁶ is selected from thegroup consisting of methyl, ethyl, isopropyl, n-propyl, n-butyl,isobutyl, sec-butyl, tert-butyl, cyclopentyl and cyclohexyl and R′ is amonovalent hydrocarbon radical having 1 to 12 carbon atoms.
 7. Theaqueous polyurethane dispersion according to claim 1, wherein thecompound (WD_(HC)) is chosen from compounds having at least one tertiaryamino group or at least one quaternary amino group.
 8. The aqueouspolyurethane dispersion according to claim 6, wherein the component(WD_(H)) present in the mixture (M) consists essentially of: i. xmmol/kg of the compound (WD_(HA)), and/or ii. y mmol/kg of the compound(WD_(HN)) wherein$\frac{{200x} + {70y}}{x + y} < {x + y} < \frac{{560x} + {248y}}{x + y}$and at least one of x or y is different from 0 and all mmol/kg are basedon the weight of all the components initially present in the mixture(M).
 9. The aqueous polyurethane dispersion according to claim 8,wherein the component (WD_(H))) comprises compound (WD_(HA)) which ispresent in a molar amount of 200 to 560 mmol/kg, based on the weight ofall the components initially present in the mixture (M).
 10. The aqueouspolyurethane dispersion according to claim 8, wherein the component(WD_(H))) comprises compound (WD_(HN)) which is present in a molaramount of 70 to 248 mmol/kg, based on the weight of all the componentsinitially present in the mixture (M).
 11. The aqueous polyurethanedispersion according to claim 7, wherein the component (WD_(H))comprises compound (WD_(HC)) which is present in a molar amount of 72 to165 mmol/kg, based on the weight of all the components initially presentin the mixture (M).
 12. The aqueous polyurethane dispersion according toclaim 7, wherein the component (WD_(H)) comprises compound (WD_(HZ))which is present in a molar amount of 75 to 300 mmol/kg, based on theweight of all the components initially present in the mixture (M). 13.The aqueous polyurethane dispersion according to claim 1, wherein theprepolymer (P) comprises unreacted isocyanate groups (NCO groups) in anamount of at most 15% by weight (% wt.) relative to total weight of theprepolymer (P).
 14. The aqueous polyurethane dispersion according toclaim 13, wherein said aqueous polyurethane dispersion further comprisesat least one compound (I), different from the polyol compound (b) anddifferent from the component (WD_(H)), having reactive groups chosenamong alcoholic hydroxyl groups or primary or secondary amino groups,and is present in a molar amount of at most 10%, relative to the totalmolar amount of the polyol compound (b) and the component (WD_(H)). 15.A method for the manufacturing of the aqueous polyurethane dispersionaccording to claim 1, which comprises dispersing the prepolymer (P) inwater.
 16. The method for the manufacturing of the aqueous polyurethanedispersion according to claim 15, wherein at least one compound (I),different from the polyol compound (b) and different from the component(WD_(H)), having reactive groups chosen among alcoholic hydroxyl groupsor primary or secondary amino groups is added after dispersing saidprepolymer (P) in water thereby forming a dispersed polyurethane polymer(polymer (PU).
 17. A process for the preparation of the prepolymer (P)for use in the method for the manufacturing of the aqueous polyurethanedispersion according to claim 15, comprising reacting in the presence ofthe b-pyrrolidone, the mixture (M) which comprises: (a) at least onepolyisocyanate compound (a), (b) at least one polyol compound (b),having a molecular weight Mw of 200 to 8000 and a hydroxyl functionalityof 1.5 to 6, (c) at least one water dispersible enhancing componenthaving at least one hydrophilic group or potentially hydrophilic group[component (WD_(H)), herein after] and comprising: i. x mmol/kg of atleast one water dispersible enhancing compound having at least oneanionic hydrophilic group or potentially anionic hydrophilic group[compound (WD_(HA)), herein after], and/or ii. y mmol/kg of at least onewater dispersible enhancing compound having at least one non-ionichydrophilic group or potentially non-ionic hydrophilic group [compound(WD_(HN)) herein after], and/or iii. z mmol/kg of at least one waterdispersible enhancing compound having at least one cationic hydrophilicgroup or potentially cationic hydrophilic group [compound (WD_(HC)),herein after], iv. w mmol/kg of at least one water dispersible enhancingcompound having at least one zwitterionic hydrophilic group orpotentially zwitterionic hydrophilic group [compound (WD_(HZ)), hereinafter], wherein$\frac{{200x} + {70y} + {72z} + {75w}}{x + y + z + w} < {x + y + z + w} < \frac{{560x} + {248y} + {165z} + {300w}}{x + y + z + w}$and at least one of x, y, z or w is different from 0 and all mmol/kg arebased on the weight of all the components initially present in themixture (M), (d) optionally, at least one isocyanate-reactive compound[compound (I)] herein after], different from the polyol compound (b) anddifferent from the component (WD_(H)), having reactive groups chosenamong an alcoholic hydroxyl group or primary or secondary amino group,and (e) optionally, at least one isocyanate monofunctional reactivecompound.
 18. A method for manufacturing a film comprising using theaqueous polyurethane dispersion of claim 1, wherein said aqueouspolyurethane dispersion is processed under the form of a film byspreading the liquid dispersion uniformly across a flat surface.
 19. Afilm obtained according to claim
 18. 20. A method for manufacturing acoating [coating (C), herein below] comprising using the aqueouspolyurethane dispersion of claim 1, wherein said aqueous polyurethanedispersion is applied to a surface or at least part of a substratesurface thereby forming a coated substrate.
 21. The method of claim 20,wherein the substrate is selected from the group consisting of wood,wood veneer, paper, paperboard, cardboard, textile, leather, nonwoven,surfaces of plastics, glass, ceramic, mineral building materials anduncoated or coated metals.
 22. A coating (C) or a coated substrateobtained according to the method of claim
 20. 23. A method of using atleast one pyrrolidone selected from the group consisting ofN-n-butylpyrrolidone, N-isobutylpyrrolidone, N-sec-butylpyrrolidone andN-tert-butylpyrrolidone as a diluent and a dispersing agent in themanufacturing of the aqueous polyurethane dispersion according to claim1 and as well as a coalescing agent thereby aiding said aqueouspolyurethane dispersion in the formation of a film or a coating.